Olefin conversion using complexes of mn,tc,and re with organoaluminum

ABSTRACT

A PROCESS FOR THE CONVERSION OF INTERNAL OLEFINIC HYDROCARBONS ACCORDING TO THE OLEFIN REACTION (E.G., THE OLEFIN DISPROPORTIONATION REACTION) AND FOR THE DOUBLE BOND ISOMERIZATION OF TERMINAL OLEFINIC HYDROCARBONS BY CONTACTING THE OLEFINIC HYDROCARBON WITH A CATALSYT COMPRISING A COORDINATION COMPLEX OF MANGANESE, TECHNETIUM, OR RHENIUM, TOGETHER WITH AN ORGANOALUMINUM ADJUVANT.

Int. Cl. C07c 3/62 US. Cl. 260-683 D 13 Claims ABSTRACT OF THEDTSCLOSURE A process for the conversion of internal olefinichydrocarbons according to the olefin reaction (e.g., the olefindisproportionation reaction) and for the double bond is-ornerization ofterminal olefim'c hydrocarbons by contacting the olefinic hydrocarbonwith a catalyst comprising a coordination complex of manganese,technetium, or rhenium, together with an organoaluminum adjuvant.

This application is a continuation-in-part of copending application Ser.No. 75,800, filed Sept. 24, 1970, now abandoned, which is a divisionalof copending application Ser. -.No. 717,026, filed Mar. 28, 1968, nowPat. 3,558,515 issued Jan. 26, 1971, which is a continuation-in-part ofcopending application Ser. No. 635,669, filed May 3, 1967, nowabandoned.

This invention relates to the conversion of olefin hydrocarbons and to ahomogeneous catalyst for such conversion. In one aspect this inventionrelates to the olefin reaction. In another aspect it relates to theconversion of olefins to other olefins having dilferent molecularweights. In an additional aspect, the invention relates to the doublebond isomerization of terminal olefin to internal olefins. In stillanother aspect it relates to a homogeneous, multicomponent catalystcomprising a coordination complex of manganese, technetium or rhenium,together with a catalytic adjuvant comprising an organometal compoundfor converting olefins to other olefins having molecular weightsdifferent from that of the starting olefin.

The term olefin reaction, as used herein, is defined as a process forthe catalytic conversion over a catalyst of a feed comprising one ormore ethylenically unsaturated compounds to produce a resulting productwhich contains at least ten percent by weight of product compounds,which product compounds can be visualized as resulting from at least oneprimary reaction, as defined below, or the combination of at least oneprimary reaction and at least one unsaturated bond isomerizationreaction, and wherein the sum of the compounds contained in saidresulting product consisting of hydrogen, saturated hydrocarbons, andcompounds which can be visualized as formed by skeletal isomerizationbut which cannot be visualized as formed by one or more of theabove-noted reactions, comprises less than twenty-five percent by Weightof the total of said resulting product. Feed components and unsaturatedbond isomers thereof are not included in the resulting product for thepurpose of determining the above-noted percentages.

In the olefin reaction, as defined above, the primary reaction is areaction which can be visualized as comprising the breaking of twoexisting unsaturated bonds between first and second carbon atoms andbetween third and fourth carbon atoms, respectively, and the formationof two new unsaturated bonds. Said first and second United tates Tatent6 F having three or more carbon atoms and a different acy-* clic monoorpolyene having three or more carbon atoms to produce different acyclicolefins; for example, the conversion of propylene and isobutylene yieldsethylene and isopentene;

(3) The conversion of ethylene and an internal acyclic monoor polyenehaving four or more carbon atoms to produce other olefins having a lowernumber of carbon atoms than that of the acyclic monoor polyene; forexample, the conversion of ethylene and 4-methylpentene- 2 yields3-methylbutene-1 and propylene;

(4) The conversion of ethylene or an acyclic monoor polyene having threeor more carbon atoms and a cyclic monoor cyclic polyene to produce anacyclic polyene having a higher number of carbon atoms than that of anyof the starting materials; for example, the conversion of cycloocteneand Z-pentene yields 2,10-tridecadiene; the conversion of1,5-cyclooctadiene and ethylene yields 1,5,9-decatriene;

(5) The conversion of one or more cyclic monoor cyclic polyenes toproduce a cyclic polyene having a higher number of carbon atoms than anyof the starting materials; for example, the conversion of cyclopenteneyields 1,6-cyclodecadiene and continued reaction can produce highermolecular weight materials;

(6) The conversion of an acyclic polyene having at least seven carbonatoms and having at least five carbonatoms between any two double bondsto produce acyclic and cyclic monoand polyenes having a lower number ofcarbon atoms than that of the feed; for example, the conversion of1,7-octadiene yields cyclohexene and ethylene; or

(7) The conversion of one or more acyclic polyenes having at least threecarbon atoms between any two double bonds to produce acyclic and cyclicmonoand polyenes generally having both a higher and lower number ofcarbon atoms than that of the feed material; for example, the conversionof 1,4-pentadiene yields 1,4-cyclohexadiene and ethylene.

New catalytic proceses have been discovered in recent years for theconversion of olefins to other olefins including products of both higherand lower molecular weight whereby olefins of relatively low value areconverted to olefins of higher value. Such conversions have heretoforebeen carried out using heterogeneous catalysts comprising compounds suchas compounds of molybdenum or tungsten and generally associated withsolid materials such as alumina or silica. It has now been found thatthese olefin conversions can be carried out in a substantiallyhomogeneous state using, as catalyst, selected coordination complexes ofmanganese, technetium or rhenium in combination with suitableorganometal catalytic adjuvants to produce olefins of increased valueincluding solid products, for example, rubber, suitable for themanufacture of tires, wire coating, footwear and other industrialproducts.

It is an object of this invention to provide a method and a homogeneouscatalyst system for the conversion of olefin hydrocarbons. It is also anobject of this invention to provide a homogeneous catalyst comprising acoordinating complex of manganese, technetium or rhenium, together withan aluminum-containing catalytic adjuvant for the olefin reaction. Stillanother object is to provide a method for converting olefins into otherolefins according to the olefin reaction. It is still a further objectof this invention to convert terminal olefins to internal olefins bymeans of double bond isomerization. The provision of a homogeneouscoordination catalyst system of manganese, technetium or rheniumtogether with an aluminum-containing catalytic adjuvant for convertingolefins into other olefins of higher and lower number of carbon atomsincluding rubbery polymers and copolymers is yet another object of theinvention. Other aspects and advantages of the invention will beapparent to one skilled in the art upon study of the disclosureincluding the detailed description of the invention.

According to the process of the invention, cyclic and acyclic olefins,preferably internal, non-tertiary acyclic olefins, and mixtures ofthese, including mixtures which forms by the admixture, under reactionconditions, of components comprising (a) A VII-B metal complexrepresented by the forwherein M is rhenium, manganese, or technetium;each X is a halogen; each (L) is represented by the formula sQ: zQ 2QQ 22% a R NR NR n Ncssa, R (CN),,,, [(RCO) CH-]-, substituted and Rgroup-substituted pyridine, unsubstituted or R group-substituted2,2'-bipyridine; each R is an aromatic or saturated aliphatichydrocarbon radical, including alkoxy and halo substituted radicals,having up to 20 carbon atoms; Q is phosphorous, arsenic, or antimony, Ris a divalent aromatic or saturated aliphatic hydrocarbon radical havingup to 20 carbon atoms, R is a divalent saturated or ethylenicallyunsaturated hydrocarbon radical having from 4 to carbon atoms; R ishydrogen or a methyl radical; R is an aromatic, saturated aliphatic, orethylenically unsaturated aliphatic radical having up to 30 carbonatoms; a is an integer from 1 to 6; b is an integer from 1 to 3; thenumber of (L) and X groups present in the complex is not greater thanthe number required for the metal to achieve the closed shell electronicconfiguration of the next higher atomic number inrt gas; x is a numberindicative of the polymeric state of the complex; m is 1 or 2; with (b)A catalytic adjuvant comprising a compound selected from:

(1) a R AlX compound,

(2) a mixture of (1) compounds,

(3) a mixture of one or more R AlX or AlX compounds with one or morecompounds represented by the formula R' MX or (4) a AlX compound,wherein each R is a saturated aliphatic or aromatic organic radical,including alkoxy and halo substituted radicals, having up to 20 carbonatoms; each X is a halogen; each M' is a metal of Group I-A, II-A, H-Bor III-A; each R is hydrogen or R; e is an integer from 1 to 3; f is 0or an integer from 1 to 2; the sum of e and f is 3; g is an integer from1 to 3; h is 0 or an integer from 1 to 2; and the sum of g and h isequal to the valence of M; and when cyclic olefins are converted and theadjuvant is (1), f is preferably 1 or 2.

The groups of metals as referred to herein are those of the PeriodicTable of Elements of Handbook of Chemistry and Physics, Chemical Rubber00., 45th Edition,

In a further embodiment of the invention we have discovered that theabove described catalysts are capable of converting terminal acrylicolefins to internal olefins by double bond isomerization. Accordingly,when terminal, acyclic olefins are contacted with the catalyst theyundergo double bond isomerization to an internal configuration as theprimary reaction. In addition, the internal olefin formed in situ thenundergoes the olefin reaction as defined above.

Some examples of R AlX, or AlX compounds are methylaluminum dichloride,dimethylaluminum fluoride, methylaluminum sesquichloride, aluminumtrichloride, ethylaluminum dichloride, aluminum tribromide,ethylaluminum sesquichloride, di 2 (ethylhexyl)aluminum bromide,phenylaluminum dichloride, (di(3-ethoxypropyl)aluminum bromide,benzylaluminum diiodide, dieicosylaluminum bromide, and the like, andmixtures thereof.

Some examples of the R MX compounds are: phenyllithium,t-butylpotassium, methylsodium, benzylrubidium, lithium hydride,anthrylcesium, lithiumaluminum hydride, ethylberyllium hydride, lithiumborohydride, methylcadmium chloride, diethylzinc, dicyclohexylmercury,dipropylzine, methylgallium dibromide, triethylaluminum,trieicosylaluminum, triethylindum, di(l2-chlorododecyl) aluminumchloride, triisopropylthallium, dimethylcalcium, dimethylstrontium,diethylbarium, and the like, and mixtures thereof. Preferred (b)components of the catalyst system are those of (1) or (2).

The formula [M,,(L),,X,,] is used herein to identify the productobtained by admixture of the rhenium, manganese, or technetium compoundwith at least one complexing agent. It should be understood, however,that the catalytic agent which has activity for the olefin conversion isthe product resulting from the admixture of the metal compound and thecomplexing agent, and the alumihum-containing compound under catalystforming conditions whether or not the components are present as indicated by the formula.

In such preparation the molar proportion of Group VII-B metal compoundto the selected ligand-forming compound can vary widely but will usuallybe in the range of from about 0.1:1 to about 10:1, preferably from about0.221 to 5:1. Any convenient temperature can be used for the mixing,avoiding excessively high temperature and excessively low temperaturesat which decomposition or crystallization would occur. The temperaturewill preferably to be in the range of about 0 to about C., morepreferably about 20 to about 60 C., for a time in a range of a fewseconds to 24 hours, preferably in the presence of a diluent, ashereinafter described.

Some examples of (L) ligands which are applicable in the (a) componentof the catalyst system of the present invention are: trimethylphosphine,tributylphosphine, trieicosylphosphine, triphenylphosphine,tribenzylphosphine, tricyclopentylarsine, tributylstibine,dimethylphenylphosphine, diethylphenylarsine, tetramethyldiphosphine,tetrabutyldiarsine, tetraethyldistibine, triphenylphosphine oxide,tricyclohexylphosphine oxide, tributylstibine oxide, triphenylphosphineoxide, tn'methylamine, tri-t-butylamine, triphenylamine,tri(6-phenylhexyl)amine, isopropyldiphenylamine, N,N,N',Ntetramethylethylenediamine, 4-vinylpyridine, pyridine,2,4-dimethylpyridine, 4,4 di t butyl-2,2'-bipyridine, 2,2'-bipyridine,butyl sulfide, phenyl sulfide, thiophene, 2,5 diethylthiophene,Ir-2111311, 1r-methallyl, vr-crotyl, acetylacetonate,1,3-diphenyl-l,3-propanedionate, 2,4 hexanedionate, 3,5 octanedionate,ethylenedinitrile, butyronitrile, 1,2-cyclohexylenedinitrile,dimethyldithiocarbamate, diethyldithiocarbamate, dibutyldithiocarbamate,diphenyldithiocarbate, and the like.

Because of the relative unavailability of technetium, the rhenium andmanganese complexes are presently preferred for the Group VH complex (a)components of the catalyst system. Because of their greater reactivitythe rhenium complexes are the most preferred of this group.

Some examples of these complexes are: Re(triphenylphosphine Ch,

Re (triphenylphosphine) OCl Re(triphenylphosphine) OBr [Re(2,4-pentanedionate) C1 Re (pyridine) I,

[Re (pyridine) Br Re triphenylpohsphine Br Re( 2,2'-bipyridine OCl,

Re 2,2-bipyridine) 001 Re 2,2'-bipyridine C1 Re 2,2'-bipyridine C1 Re2,2'-bipyridine) 1 Re (pyridine I Re (pyridine) Br Redimethylphenylphosphine) Cl Re(diethyldithiocarbamate Br Mn( 3-picolineBr Mn 4-picoline) Br Mn (pyridine) Br Mn(triphenylarsine oxide) Br Mn(triphenylphosphine oxide) Br Mn(acetonitrile) Br Mn (pyridine) Br Mn3-picoline Cl Mn (pyridine Cl Mn(triphenylarsine oxide) Cl Mn(triphenylphosphine oxide) Cl Mn(2,6-lutidine C1 Mn (triphenylphosphineoxide) I Mn (3 -picoline Br and the like and mixtures thereof.

The VII complex (a) components can be prepared by procedures which areconventionally known in the art such as by the treatment of VII-B metalhalides or oxyhalides with suitable ligand-forming materials.Bromine-containing complexes are presently preferred.

The molar proportion of the (a) component to the (b) component, to formthe catalyst system of the present invention, will generally be suchthat from about 0.1 to about 30, preferably from about 1 to about 20,and still more preferably from about 12 to about 20 moles of the (b)component are used for each mole of the (a) component.

The catalyst is prepared simply by combining the (a) component and the(b) component under conditions of time and temperature which permit thecatalytically active reaction product to be formed. Excessively hightemperatures at which some of the components tend to decompose orexcessively low temperatures at which some of the components tend tocrystallize or otherwise tend to become unreactive, should be avoided.In general, the components can be mixed within the broad temperaturerange of from about -80 to about 75 0., preferably from about 2 to about12 hours. The contact is preferably carried out in the presence of aninert solvent in which both the components are at least partiallysoluble, such as hydrocarbons and halogenated hydrocarbons applicablefor preparing the complex. Halogenated solvents are preferred andsolvents such as benzene, xylene, cyclohexane, isooctane, chlorobenzene,ethylene dichloride, methylene chloride and the like are frequentlyused. The mixing of the catalyst components is carried out in thesubstantial absence of air or moisture, generally in an inertatmosphere.

After the catalytic reaction is formed it need not be isolated but canbe added directly to the olefin conversion zone as a dispersion in itspreparation solvent. It is generally preferred that the catalystcomponents be combined prior to the contact with the feed olefin.

Olefins applicable for use in the process of the invention arenon-tertiary, non-conjugated, acyclic monoand polyenes having at least 3carbon atoms per molecule including cycloalkyl and aryl derivativesthereof, cyclic and polycyclic monoand polyenes having at least 4 carbonatoms per molecule including alkyl and aryl derivatives thereof;mixtures of the above olefins; and mixtures of ethylene and the aboveolefins. Many useful reactions are accomplished with such acyclicolefins having from 3 to 30 carbon atoms per molecule and with suchcyclic olefins having 4 to 30 carbon atoms per molecule. Non-tertiaryolefins are those wherein each carbon atom, which is attached to anothercarbon atom by means of a double bond, is also attached to a hydrogenatom. Internal olefins are preferred for the olefin reaction conversion.The above described acyclic olefins having terminal double bonds undergodouble bond rearrangement to internal olefins.

Some specific examples of acyclic olefins suitable for reactions of thisinvention include propylene, l-butene, l-pentene, Z-pentene, l-hexene,1,4-hexadiene, Z-heptene, l-octene, 2,5-octadiene, 2-nonene, l-dodecene,Z-tetradecene, l-hexadecene, 3-methyl-l-butene, l-phenylbutene- 2,allylbenzene, 3-eicosene, 3-hexene, 1,4-pentadiene, l, 4,7-dodecatriene,4 methyl 4 octene, 4-vinylcyclohexene, 1,5-octadiene, 1,5-eicosadiene,Z-triacontene, 2,6- dodecadiene, l,4,7,10,13-octadecapentaene,8-cyclopentyl- 4,5-dimethyl-1-decene, 6,6-dimethyl-1,4-octadiene, and 3-heptene, and the like, and mixtures thereof.

Some specific examples of cyclic olefins suitable for the reactions ofthis invention are cyclobutene, cyclopentene, cycloheptene, cyclooctene,S-n-propylcyclooctene, cyclodecene, cyclododecene, 3,3,5,5tetramethylcyclononene, 3,4,5,6,7-pentaethylcyclodecene,1,5-cyclooctadiene, 1,5, 9 cyclododeoatriene,1,4,7,lO-cyclododecatetraene, 4- benzylcyclohexene,6-methyl-6-ethylcyclooctadiene 1,4, and the like, and mixtures thereof.

It will be understood by those skilled in the art that not all olefinicmaterials will be converted in accordance with the olefin reaction bythe present invention with equal effectiveness. The reactions describedin the present invention are equilibrium-limited reactions and, barringthe selective removal of one or more products from the reaction zone,the extent of conversion will depend upon the thermodynamics of thespecific system observed. Thus, conversion of olefinic materials to givespecific products can be thermodynamically favored while the reversereaction is very slow and ineffective. For example, 1,7- octatriene isconverted to equilibrium-favored products such as cyclohexene andethylene. The reverse reaction of ethylene and cyclohexene,correspondingly, goes very poorly. Other well-known factors, such assteric hindrance in bulky molecules, significantly and sometimesdrastically affect the rates of reaction of some olefins suchthatextremely long reaction times are required.

The olefin reaction of symmetrical monoolefins with themselves, to givedifferent olefin products, will sometimes proceed very slowly, requiringsome double bond migration to take place before the reaction willproceed at a significant rate. For the same reason, the olefin reactionconversion of a mixture of ethylene and a l-olefin, for example, can bemore difiicult than the conversion of ethylene with an internal olefin,some double bond isomerization also being required in this instance.

It has also been found that branching also retards the olefin reactionreactivity in proportion to its propinquity to the reacting double bond.Analogously, the presence of inert polar substituents on the olefiniccompound appears tolerable only if located some distance from the doublebond. V

' Thus, the present invention is directed primarily to the conversion ofthose olefins or combination of olefins which are capable of undergoingthe olefin reaction to a significant degree when contacted with thecatalyst of the present invention under reaction conditions suitable foreffecting the olefin reaction.

When terminal acyclic olefins, in the absence of other types of olefins,are contacted with the catalyst the primary reaction involved is doublebond isomerization. The internal double bond isomer formed in situ thenundergoes the olefin reaction, including disproportionation, asdiscussed previously. However, the olefin reaction conversion proceedsmuch more slowly than the isomerization reaction when terminal olefinsare present in the reaction mixture.

Presently preferred olefinic feed compounds for the olefin reactionconversion are those contained in the following classes:

(1) Internal acyclic monoolefins, including those with aryl, cycloalkyl,or cycloalkenyl substitutents, having 4-20 carbon atoms per moleculewith no branching closer than about the 3-position and no quaternarycarbon atoms or aromatic substitution closer than the 4-pos1t1on to thedouble bond, and mixtures of such unsubstituted acyclic internalmonoolefins. Some examples of these are: butene-Z, pentene-Z, hexene-Z,hexene-3, octene-4, nonene- 2, 4-methylpentene-2, decene-3,8-ethyldecene-2, dodecene-4, eicosene-S, and the like.

(2) Acyclic, nonconjugated polyenes having from 7 to about 20 carbonatoms per molecule, containing from 2 to about 4 internal double bondsper molecule and having at least one double bond with no branchingnearer than the 3-position and no quaternary carbon atom nearer than the4-position to that double bond, or mixtures of such polyenes. Someexamples are: 2,5-heptadiene, 2,6- octadiene, 4-methyloctadiene-2,6,3,6,9,-dodecatriene, and the like.

(3) Cyclopentene.

(4) Monocyclic and bicyclic monoolefins having 7 to 12 ring carbonatoms, including those substituted with up to 3 alkyl groups having upto about 5 carbon atoms, wlth no branching closer than the 3-positionand with no quaternary carbon atoms closer than the 4'position t thedouble bond, and mixtures of such olefins including mixtures withcyclopentene. Some examples are: cycloheptene, cyclooctene,4-methylcyclooctene, 3-methyl-5-ethylcyclodecene, cyclononene,cyclododecene, norbornene, and the like.

A mixture of one or more of the monocyclic olefins of (4) with one ormore unsubstituted acyclic internal monoolefins of (1). Some examples ofthese are: hexene-3 and cycloheptene, butene-2 and cyclooctene, butene-Zand cyclodecene, pentene-2 and cyclooctene, heptene-3 and cyclodecene,and the like.

(6) Monocyclic and bicyclic polyenes having from 5 to about 12 ringcarbon atoms, including those substituted with up to 3 alkyl groupshaving up to about 5 carbon atoms, each having at least one double bondwith no branching closer than the 3-position and with no quaternarycarbon atoms closer than the 4-position to that double bond, andmixtures thereof. Some examples of these are: 1,5-cyclooctadiene,1,5,9-cyclododecattiene, 1,4-cycloheptadiene, norbornadiene, and thelike.

(7) A mixture of one or more monocyclic polyenes of (6) with one or moreof the unsubstituted acyclic internal olefins of (1). Some examples ofthese are: 1,5-cyclooctadiene and butene-Z, 1,5,9-cyclododecatriene andbutene-2, 1,5,9-cyclododecatriene and pentene-Z, and the like.

(8) Polar group-substituted olefinic compounds of classes (1) through (7containing from 6 to about 20 carbon atoms per molecule in which thepolar group, such as a halogen atom, is sufiiciently removed from theactive double bond (generally no nearer to the double bond than the5-position) so as not to interfere with the reaction, and mixtures withunsubstituted members of class (1). Some examples are: 7-chlorooctene-2,and the like.

The presently preferred feed compounds for the double bond isomerizationreaction are those contained in the following classes:

(a) Terminal acyclic monoolefins including those with aryl, cycloalkyl,or cycloalkenyl substituents, having 4-20 carbon atoms per molecule withno branching closer than about the 3-position and no quaternary carbonatoms or aromatic substitution closer than the 4-position to the doublebond, and mixtures of such unsubstituted or substituted terminalolefins. Some examples are: butene-l, pentene-l, hexene-l, octene-l,nonene-l, 4-methylpentene-l, decene-l, 8-ethyldecene-1, dodecene-l,ecosene-l, and the like.

According to the process of the invention, the olefin or mixture ofolefins to be converted in accordance with the olefin reaction or to beconverted in accordance with double bond isomerization is contacted withthe catalyst system of the present invention at any convenienttemperature; however, excessively high or excessively low temperaturesshould be avoided as stated above. Preferred temperatures are in therange of from about 30 to about 75 C., more preferably from about 0 to25 C. and at any convenient pressure which is suflicient to maintain aliquid phase. The conversion can be carried out in the presence of aninert solvent or a diluent such as that used for the catalystpreparation. Diluents are not essential but are generally preferred andsuch diluents can include saturated aliphatic and aromatic hydrocarbonssuch as cyclohexane, xylene, isooctane and the like, and derivativesthereof. The time of contact will depend upon the desired degree ofconversion, and the specific olefin feed stock and catalyst s utilizedbut will, generally, be in the range of from about 0.1 minute to 20hours, preferably 5-120 minutes. The proportion of catalyst compositionto olefin feed in the reaction zone will generally be such such about0.001-100 millimoles of Group VII-B metal will be present for each moleof olefin in the reaction zone.

Any conventional contacting technique can be utilized for the olefinconversion, and batchwise or continuous operation can be utilized. Afterthe reaction period the products can be separated and/or isolated byconventional means such as by fractionation, crystallization,adsorption, and the like. Unconverted feed material, or products not inthe desired molecular weight range, can be recycled to the reactionzone. If desired, the catalyst can be destroyed by treatment with asufficient amount of Water or alcohol prior to the separation ofproducts to inactivate the catalyst. Otherwise, after separation ofproducts, the catalyst can be recycled to the reaction zone.

The invention can be further illustrated by the following examples:

EXAMPLE I Disproportionation of pentene-2 over ReCl (triphenylphosphine)/ethylaluminum dichloride Into a dry 7-ounce pressure bottle was chargedabout 0.1 g. of ReCl -(triphenylphosphine) 10 ml. chlorobenzene, 5 ml.pentene-2, and 0.15 ml. ethylaluminum dichloride. The mixture wasstirred for minutes at room temperature, hydrolyzed with water, and theolefin content of the organic phase was analyzed by gas-liquidchromatography showing the presence of 2.2 weight percent butenes, 2.9weight percent hexenes, and 94.8 weight percent pentenes.

EXAMPLE II Disproportionation of penetene-Z over ReOCl(triphenylphosphine) /ethylaluminum dichloride In a test essentiallyidentical to that of Example I except that ReOCl (triphenylphosphine)was used as a rhenium compound, the analysis showed 2.7 weight percentbutenes, 3.9 weight percent hexenes, and 93.3 weight percent pentenes.

EXAMPLE III Disproportionation of pentene-2 over ReOBr(triphenylphosphine) /ethylaluminum dichloride In a manner similar tothat of Example I, 0.307 g. of ReOBr (tr1phenylph0sphine) and 10 ml. ofchloroben- 9 zone was chilled to C. and treated with 4 ml. of a 1 molarsolution of ethylaluminum dichloride in chlorobenzene. The solution wasthen maintained at 12 C. for 21 hours. A ml. quantity of pentene-2 wasthen added and the homogeneous solution was allowed to warm to roomtemperature with agitation. After 3 hours a sample of the reactionmixture was analyzed and found to contain about 8.9 percent butenes,about 70.8 percent pentene-Z and about 20.2 percent hexene, by weight,thus illustrating that the catalyst possessed high activity fordisproportionation of pentene-Z.

EXAMPLE IV Disproportionation of pentene-2 over rheniumcomplexes/methylaluminum sesquichloride In a manner similar to thepreceding examples additional runs were carried out to illustrate thedisproportionation of pentene-Z using methylaluminum sesquichloride(MASC) in place of ethylaluminum dichloride (EADC). In 2 hour run thecatalyst system comprising ReCL,(triphenylphosphine) +MASC was found toprovide 1% conversion to C and C olefins. In an 18 hour run, thecatalyst system comprising ReOCl (triphenylphosphine) +MASC was found toprovide 2% conversion to C and C olefins. In a 4 hour run, the catalystsystem comprising ReOBr (triphenylphosphine) +MASC was found to give 31%conversion to C and C olefins. This example demonstrates that MASC isalso a suitable component for catalysts of the present invention.

EXAMPLE V Isomerization of pentene-I A 0.2 g. quantity of ReOBr(triphenylphosphineh was charged into an 8 oz. reaction bottle followedby 10 ml. chlorobenzene, 5 ml. pentene-l, and 3 ml. of chlorobenzenesolution containing 3 millimoles of ethylaluminum dichloride. Theadditions were made in an inert nitrogen atmosphere in the absence ofair or moisture. The mixture was stirred at room temperature for about22 hours then hydrolyzed by the addition of water. Analysis of theorganic phase showed that the pentene-l had been isomerized to a mixtureof pentenes containing 18.8% cis-pentene-2, 66% trans-pentene-Z, and15.7% pentene-l, by weight. Trace amounts of butenes and hexenes werealso found indicating that some of the pentene-2, prepared in situ,underwent disproportionation.

EXAMPLE VI Isomerization of octene-l About 0.1 g. of ReCl(triphenylphosphine) 10 ml. chlorobenzene, ml. octene-l, and 0.15 ml.ethylaluminum dichloride were charged into an 8 oz. reaction bottleunder a nitrogen atmosphere. After stirring at room temperature for 90minutes, the mixture was hydrolyzed and the organic phase was analyzedby gas-liquid chromatography showing the presence of internal doublebond isomers of octene-l.

In another similar run, a reaction mixture containing about 0.1 g. ReOCl(triphenylphosphine) 10 ml. chlorobenzene, 5 ml. octene-l, and 0.15 ml.ethylaluminum dichloride was stirred 90 minutes at room temperature.Subsequent analysis showed that this catalyst system also convertedoctene-l into a mixture of octene isomers.

In the practice of the process of the invention the feed olefins,catalysts and operating conditions disclosed include combinationswherein solid, rubbery materials are produced; for example, if apropylene feed and a suitable aluminum-containing adjuvant such as anorganoaluminum dihalide or an organoaluminum sesquihalide are used, asolid, rubbery material is produced having characteristics ofethylene-propylene rubber. This rubbery material is useful in themanufacture of tires, wire coating, footwear and other industrialproducts.

The homogeneous catalysts of this invention can be deposited upon asuitable support or carrier and used in the olefin reaction, preferablywhere the olefin feed is in the vapor phase. Catalyst supports includesolid, inorganic or organic materials conventionally used as catalystsupports or carriers such as silica, alumina, silica-alumina, titania,boria, zeolites, ion exchange resins, solid polymers containingfunctional groups such as those prepared by the polymerization of4-vinylpyridine, vinyl dimethylphosphine, and the like.

The support can be impregnated with the homogeneous catalyst by wettingthe support with a solution of the catalyst in a solvent which is thenevaporated. The support can also be impregnated with either the (a) or(b) component and the remaining component can be added later. Forexample, the solid support material can be impregnated with the (a)component and the resulting composite conveniently stored untilrequired. Just prior to use, the composite can be treated with the (b)component, or, if the reaction is in the liquid phase, the (b) componentcan simply be added to the reaction zone. Among solvents suitable forrelatively low-boiling organic solvents such as pentane, methylenechloride, cyclohexane, and the like. The amount of homogeneous catalystadded to the support will be from 0.1 to about 30 weight percent of thetotal of the catalyst and support. If the support is to be activated bycalcination, it is usually activated prior to the impregnation step.

Impregnation and evaporation conditions in preparing the catalyst areconventional, being carried out at temperatures up to about C. Operatingconditions in carrying out the olefin reaction are the same for thesupported and the nonsupported homogeneous catalyst systems.

We claim:

1. A process for converting at least one feed olefin hydrocarbon havingat least 3 carbon atoms per molecule or a mixture of at least one sucholefin hydrocarbon and ethylene which comprises contacting said feedhydrocarbon or mixture under conditions suitable for converting the feedolefin by the olefin reaction and/ or isomerization to a productcomprising at least one other olefin with a catalyst system which formson admixing, under catalyst forming conditions, of components comprising(a) a coordination complex represented by the formula wherein X is ahalogen; L is a ligand selected from R P and [(RCO) CH] and, when b is 3and L is R P, one L can be 0; each R is an aromatic or saturatedaliphatic hydrocarbon radical, including alkoxy and halo-substitutedradicals, having up to 20 carbon atoms; a is an integer from 2 to 4; bis an integer from 1 to 3; and x is an integer indicative of thepolymeric state of the complex; with (b) a catalytic adjuvant comprisinga compound selected from:

(2) a mixture of 1) compounds,

(3) a mixture of one or more (1) compounds with one or more compoundsrepresented by the formula R' M'X or (4) a AlX compound,

whetrein each R is a saturated aliphatic or aromatic organic radicalhaving up to 20 carbon atoms; each X is a halogen; each M is a metal ofGroup I-A, II-A, II-B or IIIA; each R is hydrogen or R; e is an integerfrom 1 to 3; f is 0 or an integer from 1 to 2; the sum of e and f is 3;g is an integer from 1 to 3; h is 0 or an integer from 1 to 2; and thesum of g and h is equal to the valence of M.

2. The process of claim 1 wherein the feed undergoes the olefin reactionconversion and the feed olefin hydrocarbon is an internal nontertiary,nonconjugared, acyclic monoand polyene having at least 3 carbon atomsper molecule including cycloalkyl and aryl derivatives thereof, cyclicand polycyclic monoand polyenes having at least 4 carbon atoms permolecule including alkyl and aryl derivatives thereof; mixtures of theabove olefins; or mixtures of ethylene and the above olefins.

3. The process of claim 2 wherein the feed olefin hydrocarbon isselected from the group consisting of (1) internal, acyclic monoolefinsincluding those with aryl, cycloalkyl, or cycloalkenyl substituents,having 4 to 20 carbon atoms per molecule with no branching closer to thedouble bond than the 3-position and no aromatic substitution orquaternary carbon atoms closer to the double bond than the 4-positionand mixtures of such unsubstituted internal monoolefins;

(2) polyenes having from 7 to about 20 carbon atoms per molecule,containing from 2 to about 4 internal double bonds per molecule andhaving at least one double bond with no branching closer than the3-position and no quaternary carbon atom closer than the 4-position tothat double bond and mixtures of such polyenes;

(3) cyclopentene;

(4) cyclic and bicyclic monoolefins having 7 to about 12 ring carbonatoms, including those substituted with up to 3 alkyl groups having upto about 5 carbon atoms, with no branching closer to the double bondthan the 3-position and no quaternary carbon atoms closer to the doublebond than the 4-position and mixtures of such olefins and mixtures ofsuch olefins and cyclopentene;

(5) a mixture of one or more of the monocyclic olefins of (4) with oneor more unsubstituted, acyclic, internal monoolefins of 1);

(6) cyclic and bicyclic polyenes having from 5 to about 12 ring carbonatoms, including those substituted with up to 3 alkyl groups having upto about 5 carbon atoms each, having at least one double bond with nobranching closer to it than the 3-position and no quaternary carbonatoms closer to it than the 4-position and mixtures of such polyenes;and

(7) a mixture of one or more of the monocyclic polyenes of (6) with oneor more of the unsubstituted acyclic internal olefins of (l).

4. The process of claim 1 wherein the conversion produces a productaccording to the olefin reaction, which as defined herein, can bevisualized as comprising the reaction between two first pairs of carbonatoms, the two carbon atoms of each first pair being connected by anolefinic double bond, to form two new pairs from the carbon atoms ofsaid first pairs, the two carbon atoms of each said new pairs beingconnected by an olefinic double bond.

5. The process of claim 1 wherein the conversion is double bondisomerization and the feed olefin hydrocarbon is a terminal,nontertiary, nonconjugated, acyclic monoolefin.

6. The process of claim 1 wherein the molar ratio of the (b) componentof the catalyst to the (a) component of the catalyst is in the range offrom about 0.1:1 to about 20: 1.

7. The process of claim 1 wherein the conditions for the conversionreaction include a temperature in the range of from about -30 to aboutC., a pressure which is sufficient to maintain the liquid phase, a timeof contact in the range from 0.1 to about hours, and a ratio of catalystcomposition to olefin feed of from about 0.001 to 100 millimoles ofrhenium metal for each mole of olefin feed.

8. The process of claim 1 wherein the conversion is accomplished in thepresence of an inert diluent in which both of the (a) and (b) componentsof the catalyst are at least partially soluble.

9. The process of claim 1 wherein the catalyst further includes a solidinorganic or organic support or carrier selected from the groupconsisting of silica, alumina, silica-alumina, titania, boria, zeolites,ion exchange resin, a solid polymer of 4-vinylpyridine and a solidpolymer of vinyl dimethylphosphine.

10. The process of claim 1 wherein the feed olefin hydrocarbon ispentene-Z, or pentene-l.

11. The process of claim 10 wherein the (a) component is represented bythe formula ReCl (triphenylphosphine) and the (b) component isethylaluminum dichloride, or methylaluminum sesquichloride.

12. The process of claim 10 wherein the (a) component is represented bythe formula ReOCl (triphenylphosphine) and the (b) component isethylaluminum dichloride, or methylaluminum sesquichloride.

13. The process of claim 10 wherein the (a) component is represented bythe formula ReOBr (triphenylphosphine) and (b) component isethylaluminum dichloride, or methylaluminum sesquichloride.

References Cited UNITED STATES PATENTS 3,379,706 4/1968 Wilke 260683.153,457,319 7/1969 Olechowski et al. 260677 3,450,732 6/1969 Wilke et al.25243l 3,409,681 11/1968 Kroll 260-683.2 3,341,619 9/1967 Stogryn et a1.260-683.15

DELBERT E. GANTZ, Primary Examiner C. E. SPRESSER, JR., AssistantExaminer US. Cl. X.R.

26094.9 B, 658 R, 666 A, 668 R, 677 R, 680 R, 632.2

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Noe3,776,973 Dated: December i 1973 Edmund T. Kittleman and Ernest A. ZuechIt is certified that error appears in the above identiiied patent andthat said Letters Patent are hereby corrected as shown below:

COlJJnIl it, line as, delete L(R00) cH-]" and insert L(HCO) on; line 1,delete *whetrein" and insert wherein -----5 line 61, beginning w ereineach 1% is a. saturated aliphatic or" and running through line 70, "thevalence of M' should be flush with the left-hand margin. Column 11, line9, after "to" insert about Column 12, line 12, after "range" insert ofline 23, delete 'resin" and insert resins Signed and sealed this 23rd d5of April 1971 SEAL Attest:

EDWARD M ulnar-1 2. a. E-LARSHALL mm:

Attesting Officer Jommissioner of Patents

